CN1124236C - Method for fabricating silica glass - Google Patents
Method for fabricating silica glass Download PDFInfo
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- CN1124236C CN1124236C CN98103083A CN98103083A CN1124236C CN 1124236 C CN1124236 C CN 1124236C CN 98103083 A CN98103083 A CN 98103083A CN 98103083 A CN98103083 A CN 98103083A CN 1124236 C CN1124236 C CN 1124236C
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/045—Silica-containing oxide glass compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/02—Pure silica glass, e.g. pure fused quartz
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/20—Wet processes, e.g. sol-gel process
- C03C2203/22—Wet processes, e.g. sol-gel process using colloidal silica sols
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/20—Wet processes, e.g. sol-gel process
- C03C2203/30—Additives
- C03C2203/32—Catalysts
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2203/00—Production processes
- C03C2203/50—After-treatment
- C03C2203/52—Heat-treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Geochemistry & Mineralogy (AREA)
- Optics & Photonics (AREA)
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Abstract
A method for fabricating a silica glass is provided. The method includes the steps of adding silica and a dispersant to a premix solution obtained by dissolving an acrylic resin monomer and a cross-linking agent in distilled water, dispersing the mixed solution and adjusting the pH of the mixture, to form a sol. Air bubbles are removed from the sol, and then the resultant sol is aged. A polymerization initiator and a catalyst are added to the aged sol. The reaction mixture is poured into a mold, and then the mixture is gelated, aged, demolded, dried, and then thermally treated to remove organic substances and the gel is sintered. A high purity silica glass tube, substantially free of cracking after drying and having a low shrinking ratio can be obtained. Also, a large silica glass tube can be manufactured by this fabrication method.
Description
The present invention relates to make the method for silica glass by colloidal sol-gel process.
Usually, silica glass is transparent and unreactiveness is arranged to have high-caliber thermostability and intensity, and the low coefficient of expansion.Because these characteristics, silica glass is widely used in the device as optical fiber or optical lens.
In essence, optical fiber is made up of the fuse at its center and (metal) coating layer with the index of refraction that is different from fuse, so that light all reflects from fuse.In order to make optical fiber, it comprises the coating pipe of a plug and this plug of sealing a kind of optic fiber preformed article.Then, in addition thermal treatment and being elongated of optic fiber preformed article to form optical fiber.
By modified chemical vapor deposition (MCVD) method, vapor phase axial deposition (VAD) method or outer vapour deposition (OVD) manufactured optic fiber preformed article.
In chemical vapour deposition, optic fiber preformed article is to be made by the coating pipe that high-purity quartz glass is made.Here, the coating pipe of silica glass forms by colloidal sol-gel process.
Colloidal sol-gel process as a kind of liquid phase process, can improve the component that output is also freely controlled product.And because colloidal sol-gel process carries out at low temperatures, this colloidal sol-gel process is the method for very economical.And because high purity material is used as starting material, this method is widely used in makes semiconductor light mask and high-purity quartz glass.
Below the concise and to the point method of making the coating pipe that silica glass forms by colloidal sol-gel process of describing.
At first, silicon grain is scattered in the water to form colloidal sol.The colloidal sol that forms is through the burin-in process of the scheduled time.Then, pour the colloidal sol that produces into mold and carry out gelation.Finish after the gelation, from mold, isolate gel and make it dry.
Then, the exsiccant gel is heat-treated so that remove organic substance from gel.Then, from the gel of removing organic substance, eliminate the reaction of oh group, and carry out a sintering process, thereby finished the coating pipe of making by silica glass.
The speed of response of above-described colloidal sol-gel process depends on component, pH and the solvent of gelation reaction temperature, colloidal sol, is difficult to keep speed of response in OK range by controlling these factors.In addition, when molded gel drying, can produce many crackles, and in sintering, shrinkage and crackle can take place.In order to address these problems, developed a kind of dry control chemical additive (DCCA) or a kind of polymer-bonded agent method, or redispersion method and supercritical drying drying method.
Use method local difference the vaporator rate of solvent from gel of dry control chemical additive (DCCA) to minimize, thereby in drying process, also the difference of the local pressure of sample is minimized.Its result.Therefore the gel hardening has reduced cracking.
According to the redispersion method, the exsiccant fine silica powder, the silicon that promptly atomizes is scattered in and forms colloidal sol in the water, colloidal sol gelling subsequently.In gelatinization process, because hydrogen bond makes silicon grain form a kind of agglomerate.After the agglomerate drying, the exsiccant agglomerate stand thermal technology's preface and grinding step subsequently redispersion in water.The gelling in addition of the product of redispersion, molded sintering then.
Yet aforesaid method be not effectively preventing aspect the crackle, and preparation process is very complicated in the Drying of gels process.
In order to solve the above problems, the object of the present invention is to provide the method for making the high-density silica glass, after the drying process crackle taking place and got rid of, and has also reduced generation crackle and contraction after sintering circuit in this method.
Therefore, in order to reach the above object, provide a kind of method of making silica glass, it comprises following steps:
(1) silicon and a kind of dispersion agent are added to a kind of acrylic resin monomer of being dissolved in the distilled water and a kind of linking agent and a kind of aqueous premix of obtaining, disperse this mixing solutions, adjust the pH value of mixture, to form a kind of colloidal sol;
(2) from colloidal sol, remove bubble, make the colloidal sol that is produced aging then;
(3) in the colloidal sol that burin-in process is crossed, add a kind of polymerization starter and a kind of catalyzer, and the pH value of conditioned reaction mixture;
(4) this reaction mixture is poured in the mold, made the mixture gelation then;
(5) gel that obtains is made it aging;
The gel demoulding of (6) burin-in process being crossed makes the gel drying of the demoulding subsequently;
(7) the exsiccant gel is heat-treated to remove organic substance from gel; And
(8) gel of removing organic substance is carried out oh group and eliminate reaction and sintering reaction.
Below accompanying drawing is made brief description.
With reference to accompanying drawing, most preferred embodiment is described in more detail, will make above-mentioned purpose of the present invention and advantage become distincter:
Fig. 1 shows the schema of making the silica glass method by the present invention.
According to the method that the present invention makes quartz glass, chemical gelatification is that silicon is added to dissolving A kind of acrylic resin monomer of Yu Shuizhong and a kind of crosslinking agent and in the aqueous premix that obtains, And disperseed and polymerization and thermally gelling are to add a kind of gelling in the component of quartz glass Agent and the suitable pH value of adjusting products therefrom, both carry out simultaneously. Its result is set by acrylic compounds The polymer adhesive with 3-dimension network structure that alicyclic monomer and crosslinking agent form is at whole gel In evenly distribute, therefore, can eliminate the common density gradient that is caused by colloidal sol-gel process Problem. And, the intensity enhancing of gel, thereby eliminated crackle and the contracting that produces between dry period Lacked drying time.
Preferably, the acrylic monomer inclusion accounts for take the 2-20 of aqueous premix weight as base (weight) %, crosslinking agent then account for take 0.05-1.0 (weight) % of aqueous premix weight as base.
Preferably, the concentration that contains the aqueous premix of acrylic resin monomer and crosslinking agent is wanted Low. If the concentration of aqueous premix is lower, in colloidal sol-gel process at the organic substance branch Do not retain carbon after separating, then after sintering circuit the transparency of quartz glass with regard to variation. In addition Outward, if use this dilution aqueous premix, moist gel just becomes smoothly, by control The pH value is carried out the intensity that Thermogelling can improve moist gel.
There is no particular limitation to acrylic resin monomer and crosslinking agent. Yet, the acrylic compounds tree Alicyclic monomer is acrylamide or Methacrylamide preferably, and crosslinking agent N preferably, the N-methylene Base diacrylamine [(H2C＝CHCONH)
2CH
2]。
Preferably, the mixed proportion of silica and aqueous premix is based on 4 of weight: 6-6: 4.
Describe the method that the present invention makes quartz glass in detail referring to Fig. 1.
At first, a kind of acrylic resin monomer and a kind of crosslinking agent are dissolved in deionized water with system Standby aqueous premix. In aqueous premix, add atomizing silicon and dispersant, disperseed subsequently, The pH value of reactant mixture is adjusted to 11-13 to form colloidal sol.
Subsequently, use vavuum pump from colloidal sol, to remove bubble, and colloidal sol is carried out the old of the scheduled time Change is with the silicon grain of stable sol.
Subsequently, in this reactant mixture, add polymerization initiator and catalyst, also want if need Add gelling agent. Subsequently, the pH value of reactant mixture is adjusted to 9-11. Mixed with what obtain Compound is poured into and is carried out gelation in the mold. Here, preferably use N, N, N ', N '-tetramethylene Diamines (TEMED) is as catalyst.
Subsequently, at room temperature carry out after the gel burin-in process the moist gel demoulding. Exist subsequently Make it dried in the 20-50 ℃ of insulating box and under relative humidity (RH) 70-95% Dry. Then, in air, with 50 ℃ speed per hour gel is heated to 300-700 ℃, kept this temperature 2-8 hour. Then in chlorine gas environment with temperature with per hour 100 ℃ speed is elevated to 800-1200 ℃, and under this temperature gel is carried out Heat treatment continues 1-8 hour. In helium environment with temperature with 100 ℃ speed per hour Rate is increased to 1100-1500 ℃, and under this temperature gel is carried out 1-8 hour Heat treatment to form quartz glass tube.
According to the present invention, below the embodiment of the method for silica glass is made in explanation.Yet the present invention is not limited to following examples.
Embodiment 1
With the N of acrylamide and 0.6 (weight) % of 14.0 (weight) %, N '-methylene diacrylamine is dissolved in the deionized water of 85.4 (weight) % with the preparation aqueous premix.
With 500 milliliters of aqueous premix, the TMA (TriMethylAmine) hydroxide aqueous solution (accounting for the aqueous solution 25.0 (weight) %) of 500 gram atomizing silicon (the product A erosil OX-50 of Degussa company) and 52 milliliters uses strong shear mixer to mix and disperse to prepare colloidal sol.Then, from colloidal sol, remove bubble, and carry out wearing out in 15 hours with vacuum pump.6 milliliters of ammonium persulfate aqueous solutions (5 (weight) % aqueous solution) are added as catalyzer as polymerization starter and 2 milliliters of TEMED (N, N, N ', N '-tetramethylene-diamine) and mix with colloidal sol that burin-in process is crossed.
Mixture is poured into and is carried out gelation in the mold.After 30 minutes, with the wet gel stripping that obtains, 30 ℃ of thermostat containers and 90% time drying of relative humidity (RH) 4 days.Subsequently, gel is heated to 100 ℃, and under this temperature, keeps 10 hours removing residual moisture, thereby form the exsiccant gel with 10 ℃ speed per hour.
Subsequently, the exsiccant gel is heated to after 600 ℃, at 600 ℃ gel is carried out 5 hours thermal treatment, from the exsiccant gel, to remove organic substance in speed with 50 ℃/hour.The gel of removing organic substance is heated to 1000 ℃ with 100 ℃/hour speed makes it to form vitrifying.Here be in chlorine gas environment, to form glass to remove oh group.
At last, the speed with 100 ℃/hour in helium environment is heated to 1400 ℃ with products therefrom, and under this temperature gel is carried out 4 hours sintering, to form quartz glass tube.
Embodiment 2
With the N of acrylamide and 0.6 (weight) % of 12 (weight) %, N '-methylene diacrylamine is dissolved in the deionized water of 87.5 (weight) % with the preparation aqueous premix.
With 2000 milliliters of aqueous premix, TMAH (TMA (TriMethylAmine) oxyhydroxide) aqueous solution (25.0 (weight) % aqueous solution) of 2000 gram atomizing silicon (the product A erosil OX-50 of Degussa company limited) and 222 milliliters mixes and uses strong shear mixer to disperse to prepare colloidal sol.Then, use vacuum pump from colloidal sol, to remove bubble, and carry out wearing out in 15 hours.With 24 milliliters of ammonium persulfate aqueous solutions (25.0 (weight) % aqueous solution) as polymerization starter, and 6 milliliters of TEMED (N, N, N ', N '-tetramethylene-diamine) add as catalyzer and and the colloidal sol crossed of burin-in process mix.
Pour mixture into mold to carry out gelation.After 60 minutes, with the wet gel stripping that obtains, 25 ℃ of thermostat containers and 75% time drying of relative humidity (RH) 6 days.Subsequently, gel is heated to 120 ℃, and under this temperature, keeps 5 hours removing residual moisture, thereby form the exsiccant gel with 10 ℃ speed per hour.
Subsequently, the exsiccant gel is heated to 550 ℃, under 550 ℃, desiccant gel is carried out 5 hours thermal treatment, from the exsiccant gel, to remove organic substance in speed with 50 ℃/hour.The gel of removing organic substance is heated to 1000 ℃ and keep 5 hours to form glass with 100 ℃/hour speed.Here, be under chlorine gas environment, to form glass to remove oh group.
At last, products therefrom speed with 100 ℃/hour in helium environment is being heated to 1400 ℃, and under this temperature, gel is being carried out 4 hours sintering, to form quartz glass tube.
Embodiment 3
With the N of acrylamide and 0.2 (weight) % of 4.8 (weight) %, N '-methylene diacrylamine is dissolved in the deionized water of 87.5 (weight) % with the preparation aqueous premix.
With 1000 milliliters of aqueous premix, the TMAH aqueous solution (25.0 (weight) % aqueous solution) of 1100 gram atomizing silicon (the product A erosil OX-50 of Degussa company limited) and 116 milliliters mixes and uses strong shear mixer to disperse to prepare colloidal sol.Then, use vacuum pump from colloidal sol, to remove bubble, and carry out wearing out in 15 hours.With 14 milliliters of ammonium persulfate aqueous solutions (5 (weight) % aqueous solution) as polymerization starter, and 3 milliliters of TEMED add as catalyzer and and the colloidal sol crossed of burin-in process mix.
Pour mixture into mold to carry out gelation.After 60 minutes, with the wet gel stripping that obtains, 25 ℃ of thermostat containers and 75% time drying of relative humidity (RH) 6 days.Subsequently, gel is heated to 120 ℃, and under this temperature, keeps 5 hours removing residual moisture, thereby form the exsiccant gel with 20 ℃ speed per hour.
Subsequently, with 50 ℃/hour speed the exsiccant gel is heated to 550 ℃, gel carries out 5 hours thermal treatment to remove organic substance in the desiccant gel under 550 ℃.The gel of having removed organic substance is heated to 1000 ℃ with 100 ℃/hour speed, keeps making it to form in 5 hours glass under this temperature.Here, be under chlorine gas environment, to form glass to remove oh group.
At last, with speed in helium environment products therefrom is heated to 1450 ℃, and under this temperature, gel is carried out 4 hours sintering, to form quartz glass tube with 100 ℃/hour.
Embodiment 4
With the acrylamide of 4.8 (weight) % and, the N of 0.2 (weight) %, N '-methylene diacrylamine are dissolved in the deionized water of 95.0 (weight) % with the preparation aqueous premix.
With 500 milliliters of aqueous premix, the TMAH aqueous solution (25 (weight) % aqueous solution) of 500 gram atomizing silicon (the product A erosil OX-50 of Degussa company limited) and 52 milliliters mixes and disperses to prepare colloidal sol with strong shear mixer.Then, use vacuum pump from colloidal sol, to remove bubble, and carry out wearing out in 10 hours.Will be as 8 milliliters of ammonium persulfate aqueous solutions (5 (weight) % aqueous solution) of initiator with as 2 milliliters of TEMED of catalyzer and 8 gram methyl formates (is 1.6 (weight) % of base with silicon weight) are added and with through the solution mixing of burin-in process.
Pour mixture into mold to carry out gelation.The moist gel demoulding that contains to obtaining after 60 minutes reaches 75% time drying of relative humidity (RH) 6 days in 25 ℃ of thermostat containers.Then, gel is heated to 120 ℃, and under this temperature, keeps 7 hours removing residual moisture, thereby form the exsiccant gel with 20 ℃ speed per hour.
Subsequently, with 50 ℃/hour speed the exsiccant gel is heated to 550 ℃, gel is heated to 550 ℃ and keeps 5 hours with organic substance in the gel of removing.The gel that to remove organic substance with 100 ℃/hour speed is heated to 1000 ℃, keeps making it to form in 5 hours glass under this temperature.Here, be in chlorine gas environment, to form glass to remove oh group.
At last, the speed with 100 ℃/hour in helium environment is heated to 1400 ℃ with resultant, and under this temperature gel is carried out 4 hours sintering, to form quartz glass tube.
Embodiment 5
Except using methyl lactate substituent methyl methyl esters, make quartz glass tube as the method described in the embodiment 4.
Embodiment 6
Except using ethyl lactate substituent methyl methyl esters, prepare quartz glass tube as the method described in the embodiment 4.
Embodiment 7
With the Methacrylamide of 2.2 (weight) %, the N of 0.13 weight %, N '-methylene diacrylamine are dissolved in the deionized water of 96.67 (weight) % with the preparation aqueous premix.
With 500 milliliters of these aqueous premix, the TMAH aqueous solution (25 (weight) % aqueous solution) of 500 gram atomizing silicon (the product A erosil OX-50 of Degussa company limited) and 52 milliliters mixes with strong shear mixer and disperses to prepare colloidal sol.
Then, use vacuum pump from colloidal sol, to remove bubble, and place aging carrying out 10 hours.Add 8 milliliters of ammonium persulfate aqueous solutions (5 (weight) % aqueous solution) as polymerization starter, 2 milliliters of TEMED also and through aged colloidal sol mix as catalyzer and 8 gram methyl formates (is fiduciary point 1.6 (weight) % with silicon weight).Then, the mixture that obtains is poured into the shape that becomes to be scheduled to gelling in the mold.
After gelling, the moist gel that obtains is carried out the demoulding, in 30 ℃ of thermostat containers and 90% time drying of relative humidity (RH) 10 days.Then, gel is heated to 700 ℃, and under this temperature, kept 4 hours with 50 ℃ speed per hour.Then, with 100 ℃/hour speed the exsiccant gel is heated to 1100 ℃, the exsiccant gel is 1100 ℃ of thermal treatments of carrying out 5 hours.Here, heat treatment step carries out the oh group that retains with removal in chlorine gas environment.
At last, products therefrom is heated to 1500 ℃, under this temperature, gel is carried out 5 hours sintering, to form quartz glass tube with speed in helium environment with 100 ℃/hour.
Embodiment 8
Except the ethyl lactate substituent methyl formic acid that uses 10 grams, make quartz glass tube as embodiment 7 described methods.
Embodiment 9
With the Methacrylamide of 14.0 (weight) %, the N of 0.6 (weight) %, N '-methylene diacrylamine are dissolved in the deionized water of 85.4 (weight) % with the preparation aqueous premix.
With 500 milliliters of these aqueous premix, the TMAH aqueous solution (25 (weight) % aqueous solution) of 500 gram atomizing silicon (the product A erosil OX-50 of Degussa company limited) and 52 milliliters mixes and uses strong shear mixer to disperse to prepare colloidal sol.
Then, use vacuum pump from colloidal sol, to remove bubble, and placed aging 15 hours.Add 6 milliliters of ammonium persulfate aqueous solutions (5 (weight) % aqueous solution) to the gel that wore out, and from reaction mixture, remove air bubble.Then, add 2 milliliters of TEMED as catalyzer and and reaction mixture.Then, the mixture that obtains is poured into made it gelling in the mold and form predetermined shape.
After gelling, the moist gel that obtains is carried out the demoulding, in 35 ℃ of thermostat containers, reach 70% time drying of relative humidity (RH) 4 days.Then, resultant is heated to 100 ℃, and under this temperature, keeps the moisture that retained with removal in 10 hours with 10 ℃ speed per hour.
Then, the exsiccant gel is heated to 600 ℃, the exsiccant gel was heat-treated 5 hours at 600 ℃ in speed with 50 ℃/hour.Then, gel is heated to 1000 ℃, and under this temperature, kept 5 hours with 100 ℃/hour speed.Here, heat treatment step carries out the oh group that retains with removal in chlorine gas environment.
At last, with speed in helium environment products therefrom is heated to 1400 ℃, and under this temperature, gel is carried out 4 hours sintering, to form quartz glass tube with 100 ℃/hour.
Embodiment 10
With the Methacrylamide of 12.0 (weight) %, the N of 5.0 (weight) %, N '-methylene diacrylamine are dissolved in the deionized water of 83.0 (weight) % with the preparation aqueous premix.
With 2000 milliliters of these aqueous premix, the TMAH aqueous solution (25 (weight) % aqueous solution) of 2000 gram atomizing silicon (the product A erosil OX-50 of Degussa company limited) and 52 milliliters mixes and uses strong shear mixer to disperse to prepare colloidal sol.
Then, use vacuum pump from colloidal sol, to remove bubble, and place and wore out in 15 hours, add 24 milliliters of ammonium persulfate aqueous solutions (5 (weight) % aqueous solution) to the aged gel, and from reaction mixture, remove air bubble.Then, add 6 milliliters TEMED as catalyzer and and reaction mixture.Then, the mixture that obtains is poured into made it gelling in the mold and form predetermined shape.
After gelling, the moist gel that obtains is carried out the demoulding, in 25 ℃ of thermostat containers, reach 75% time drying of relative humidity (RH) 6 days.Then, resultant is heated to 120 ℃, and under this temperature, keeps the moisture that retained with removal in 10 hours with 10 ℃ speed per hour.
Then, the exsiccant gel is heated to 550 ℃, the exsiccant gel is carried out thermal treatment in 5 hours at 550 ℃ in speed with 50 ℃/hour.Then, gel is heated to 1000 ℃, and under this temperature, kept 5 hours with 100 ℃/hour speed.Here, in chlorine gas environment, heat-treat the oh group that operation retains with removal.
At last, with speed in helium environment institute's resultant is heated to 1400 ℃, and under this temperature, gel is carried out 4 hours sintering, to form quartz glass tube with 100 ℃/hour.
Embodiment 11
With the Methacrylamide of 4.8 (weight) %, the N of 0.2 (weight) %, N '-methylene diacrylamine are dissolved in the deionized water of 95.0 (weight) % with the preparation aqueous premix.
With 1000 milliliters of these aqueous premix, the TMAH aqueous solution (25 (weight) % aqueous solution) of 1000 gram atomizing silicon (the product A erosil OX-50 of Degussa company limited) and 116 milliliters mixes and uses strong shear mixer to disperse to prepare colloidal sol.
Then, use vacuum pump from colloidal sol, to remove bubble, and place and wore out in 15 hours.14 milliliters ammonium persulfate aqueous solutions (5 (weight) % aqueous solution) are added aged colloidal sol, from reaction mixture, remove air bubble.Then, add 3 milliliters of TEMED as catalyzer and and reaction mixture.The mixture that obtains is poured into the shape that makes it gelling in the mold and form needs.
After 60 minutes, the moist gel that obtains is carried out the demoulding, in 25 ℃ of thermostat containers, reach 75% time drying of relative humidity (RH) 6 days.Then, products therefrom is heated to 120 ℃, and under this temperature, keeps the moisture that retained with removal in 5 hours with 20 ℃ speed per hour.
Then, the exsiccant gel is heated to after 550 ℃, the exsiccant gel is carried out thermal treatment in 5 hours at 550 ℃ in speed with 50 ℃/hour.Then, gel is heated to 1000 ℃, and under this temperature, kept 5 hours with 100 ℃/hour speed.Here, in chlorine gas environment, heat-treat the oh group that operation retains with removal.
At last, institute's resultant is heated to 1450 ℃, under this temperature, gel is carried out 4 hours sintering, to form quartz glass tube with speed in helium environment with 100 ℃/hour.
The intensity of the gel that embodiment 1 to 11 is made is estimated.According to the result, find that gel-strength strengthens, thereby be convenient to the gel operation.
In addition, notice also whether the quartz glass tube of observing embodiment 1 to 11 manufacturing has produced crackle and contraction problem.
Consequently, in the quartz glass tube of embodiment 1-11 manufacturing, all reduced at dry and contraction back crackle.
According to silica glass making method of the present invention, can obtain the high-purity quartz glass pipe, it is few crackle that takes place after drying, and shrinks also and significantly reduce.In addition, can make large-scale quartz glass tube by this making method.
The silica glass that obtains according to making method of the present invention can be applied to semiconducter device, optical lens etc. and optic fiber preformed article.
Claims (9)
1. method of making silica glass comprises following steps:
(1) silicon-dioxide and a kind of dispersion agent are added to a kind of acrylic resin monomer of being dissolved in the distilled water and a kind of linking agent and a kind of aqueous premix of obtaining, disperse this mixing solutions, the pH value of adjusting mixture is to 11-13, to form a kind of colloidal sol;
(2) from colloidal sol, remove bubble, make the colloidal sol that is produced aging then;
(3) in the colloidal sol that burin-in process is crossed, add a kind of polymerization starter and a kind of catalyzer, and the pH value of conditioned reaction mixture is to 9-11;
(4) this reaction mixture is poured in the mold, made the mixture gelation then;
(5) gel that obtains is made it aging;
The gel demoulding of (6) burin-in process being crossed makes the gel drying of the demoulding subsequently;
(7) the exsiccant gel is heat-treated to remove organic substance from gel; And
(8) gel of removing organic substance is carried out oh group and eliminate reaction and sintering reaction.
2. in accordance with the method for claim 1, it is characterized in that in the step (3) except that polymerization starter and catalyzer, also adding a kind of jelling agent.
3. in accordance with the method for claim 2, it is characterized in that jelling agent is to be selected from a kind of compound in the group of being made up of methyl-formiate, methyl lactate and ethyl lactate at least.
4. in accordance with the method for claim 1, it is characterized in that acrylic resin monomer inclusion is 2-20 (weight) % of aqueous premix weight.
5. in accordance with the method for claim 1, it is characterized in that the inclusion of this linking agent is based on the 0.05-1.0 of aqueous premix weight (weight) %.
6. in accordance with the method for claim 1, it is characterized in that this acrylic resin monomer is to be selected from a kind of compound in the group of being made up of acrylamide or Methacrylamide at least, and this linking agent is N, N '-methylene diacrylamine.
7. in accordance with the method for claim 1, the blending ratio that it is characterized in that silicon-dioxide and aqueous premix is based on 4 of weight: 6-6: 4.
8. in accordance with the method for claim 1, it is characterized in that this catalyzer is N, N, N ', N '-tetramethylene-diamine.
9, in accordance with the method for claim 1, it is characterized in that this polymerizing agent initiator is an ammonium persulphate.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR97-35698 | 1997-07-29 | ||
| KR19970035698 | 1997-07-29 | ||
| KR9735698 | 1997-07-29 | ||
| KR9819262 | 1998-05-27 | ||
| KR1019980019262A KR100252184B1 (en) | 1997-07-29 | 1998-05-27 | Method of manufacturing silica glass |
| KR98-19262 | 1998-05-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1210824A CN1210824A (en) | 1999-03-17 |
| CN1124236C true CN1124236C (en) | 2003-10-15 |
Family
ID=26632966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98103083A Expired - Fee Related CN1124236C (en) | 1997-07-29 | 1998-07-29 | Method for fabricating silica glass |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5919280A (en) |
| JP (1) | JP2923292B2 (en) |
| KR (1) | KR100252184B1 (en) |
| CN (1) | CN1124236C (en) |
| CA (1) | CA2243879C (en) |
| FR (1) | FR2766814B1 (en) |
| GB (1) | GB2327670B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100322132B1 (en) | 1999-01-29 | 2002-01-29 | 윤종용 | Silica glass composition for sol-gel process |
| WO2000046622A1 (en) * | 1999-02-05 | 2000-08-10 | Corning Incorporated | Optical fiber component with shaped optical element and method of making same |
| KR20000074724A (en) * | 1999-05-25 | 2000-12-15 | 윤종용 | Manufacturing method of silica glass for sol-gel process |
| KR100586611B1 (en) * | 1999-06-25 | 2006-06-02 | 대우전자부품(주) | A apparatus for display tilt of deflection yoke |
| KR100318949B1 (en) * | 1999-12-16 | 2002-01-04 | 윤종용 | Fabrication method of high purity silica glass by sol-gel process |
| KR100346112B1 (en) | 1999-12-22 | 2002-08-01 | 삼성전자 주식회사 | Apparatus and method for sintering over-jacketting tube in zone sintering process of optical fiber preform fabrication process using sol-gel process |
| KR100326174B1 (en) * | 1999-12-31 | 2002-02-27 | 윤종용 | Fabrication method of high purity silica glass by sol-gel process |
| KR20050080879A (en) * | 2004-02-11 | 2005-08-18 | 삼성전자주식회사 | Method for fabricating holey fiber preform |
| KR20050080875A (en) * | 2004-02-11 | 2005-08-18 | 삼성전자주식회사 | Method for fabricating photonic crystal fiber preform |
| JP4678731B2 (en) * | 2005-09-09 | 2011-04-27 | 株式会社リコー | Manufacturing method of honeycomb structure or fine composite part |
| CN111018321A (en) * | 2019-12-31 | 2020-04-17 | 北京工业大学 | Method for preparing glass through 3D printing and photocuring molding |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4426216A (en) * | 1982-01-06 | 1984-01-17 | Hitachi, Ltd. | Process for producing optical glass |
| GB2113200B (en) * | 1982-01-08 | 1985-06-19 | Hitachi Ltd | Process for producing optical glass |
| JPS6385018A (en) * | 1986-09-26 | 1988-04-15 | Harima Ceramic Co Ltd | Production of high purity silica glass |
| JPH0825754B2 (en) * | 1986-10-31 | 1996-03-13 | セイコーエプソン株式会社 | Glass manufacturing method |
| JPH01176234A (en) * | 1987-12-29 | 1989-07-12 | Hitachi Chem Co Ltd | Production of silicate glass |
| IL93134A (en) * | 1990-01-23 | 1997-11-20 | Yissum Res Dev Co | Doped sol-gel glasses for obtaining chemical interactions |
| DE4130440A1 (en) * | 1991-09-13 | 1993-03-18 | Philips Patentverwaltung | METHOD FOR PRODUCING MOLDED BODIES FROM CERAMIC OR GLASS |
| US5240488A (en) * | 1992-08-14 | 1993-08-31 | At&T Bell Laboratories | Manufacture of vitreous silica product via a sol-gel process using a polymer additive |
-
1998
- 1998-05-27 KR KR1019980019262A patent/KR100252184B1/en not_active IP Right Cessation
- 1998-07-27 US US09/122,627 patent/US5919280A/en not_active Expired - Fee Related
- 1998-07-27 CA CA002243879A patent/CA2243879C/en not_active Expired - Fee Related
- 1998-07-27 JP JP10211239A patent/JP2923292B2/en not_active Expired - Fee Related
- 1998-07-28 GB GB9816329A patent/GB2327670B/en not_active Expired - Fee Related
- 1998-07-28 FR FR9809640A patent/FR2766814B1/en not_active Expired - Fee Related
- 1998-07-29 CN CN98103083A patent/CN1124236C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990013379A (en) | 1999-02-25 |
| GB9816329D0 (en) | 1998-09-23 |
| US5919280A (en) | 1999-07-06 |
| JPH11116245A (en) | 1999-04-27 |
| GB2327670A (en) | 1999-02-03 |
| CA2243879C (en) | 2001-07-03 |
| CN1210824A (en) | 1999-03-17 |
| FR2766814A1 (en) | 1999-02-05 |
| GB2327670B (en) | 1999-06-16 |
| JP2923292B2 (en) | 1999-07-26 |
| CA2243879A1 (en) | 1999-01-29 |
| FR2766814B1 (en) | 2000-12-22 |
| KR100252184B1 (en) | 2000-04-15 |
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